CN113318794B - Preparation method and application of plasmon composite photocatalyst Pd/DUT-67 - Google Patents
Preparation method and application of plasmon composite photocatalyst Pd/DUT-67 Download PDFInfo
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- 239000013432 DUT-67 Substances 0.000 title claims abstract description 84
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 21
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- 230000001699 photocatalysis Effects 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 11
- 239000004809 Teflon Substances 0.000 claims description 10
- 229920006362 Teflon® Polymers 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 9
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
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- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
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- 101150003085 Pdcl gene Proteins 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/23—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
The invention belongs to the technical field of preparation of environmental materials, and relates to a preparation method and application of a plasmon composite photocatalyst Pd/DUT-67. The present invention includes (1) the preparation of DUT-67; (2) preparing Pd nanosheets; (3) and preparing the plasmon composite photocatalyst Pd/DUT-67. The method prepares DUT-67 through solvothermal method, prepares Pd nanosheets through oil bath reduction method, finally prepares Pd/DUT-67 composite photocatalyst through solvothermal method, and improves CO by utilizing DUT-67 with porous structure and large specific surface area2The adsorption amount provides a dispersing position for the noble metal Pd, and the Pd improves the photoelectric conversion capacity, the light absorption capacity and the selective catalytic conversion of CO of the Zr-MOFs2And (4) performance. The invention realizes the efficient reduction of CO by the plasmon composite photocatalyst Pd/DUT-67 composite photocatalyst2The purpose of (1).
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials, and relates to a preparation method and application of a plasmon composite photocatalyst Pd/DUT-67.
Background
Currently, more than 80% of the global energy consumption is dependent on fossil fuels driven by global population growth and industrialization. By 2040, global energy consumption will increase by 56%. Over-exploitation of fossil fuels leads to CO in addition to reducing natural energy reserves2The amount of emissions increases greatly. CO in the atmosphere2Concentration levels have exceeded 400ppm (a 40% increase over 1750 years) and have grown at a rate of about 2ppm per year. It is estimated that by 2030, CO is emitted to the atmosphere2Up to 402 million tons. And excessive CO2Causes a range of environmental problems such as global warming, ocean acidification, extreme weather and species extinction. Thus, the dioxide is captured simply, economically and efficientlyCarbon and its conversion to other chemical forms is critical.
Solar energy is a renewable energy source, and CO is driven by utilizing the solar energy at normal temperature and normal pressure2The light reduction is carried out to convert the carbon into chemicals or liquid fuels with high added value, the method has the advantages of low energy consumption, low cost, no pollution and the like, and the carbon resource recycling and the energy economy development are realized while the greenhouse gas emission is reduced. But due to CO2Cannot absorb visible light and ultraviolet light with the wavelength of 200-900nm, so that CO2The photocatalytic reduction of (a) must be by means of a catalyst. CO reported to date2The reduction photocatalyst comprises oxide, sulfide, polymer material, double-layer hydroxide and the like, and although the carbon dioxide photocatalytic materials reported in the literature are large in quantity and variety, the traditional semiconductor catalyst has limited specific surface area and CO2The low adsorption capacity results in a photocatalytic performance that is still not ideal. In the photocatalytic reduction of CO2In the process of (2), when CO is present2Subsequent electron transfer to the adsorbed CO after adsorption and activation on the catalyst surface2In this way, a series of chemical reactions are initiated, ultimately determining the distribution of the products and the efficiency of the photocatalytic process, and therefore CO2Adsorption and activation on the catalyst surface are critical for the subsequent reduction reaction. Thereby developing higher CO2The absorbed photocatalyst is CO2The primary task of photocatalytic conversion.
Metal Organic Frameworks (MOFs) are a novel class of porous materials useful for gas separation, storage, and catalysis. Due to the large specific surface area, the large space inside and outside the channel enables the CO of the MOFs2The adsorption capacity is greatly improved. MOFs selectively adsorb CO2Molecules, enrichment of CO around the photocatalytically active center2Molecule, thereby effectively promoting photocatalytic CO2Reduction reaction occurs. Zr-MOFs have stronger metal-coordination bonds, and the stability of a framework can be enhanced through inorganic nodes with high connectivity, but the catalytic active sites of the Zr-MOFs cannot be fully utilized, so that the utilization rate of visible light is low, and the Zr-MOFs are limited in CO2Catalytic efficiency in photoreduction. Thus, the Zr-MOFs can be further improved by means of noble metalsPhysical and chemical properties and photoelectric properties, and can improve the photocatalytic reduction of CO2Conversion efficiency and selectivity.
The local surface plasmon resonance phenomenon of the noble metal macroscopically shows that the noble metal strongly absorbs light with specific wavelength, so that the response range of the photocatalyst for absorbing light wavelength can be widened through the local surface plasmon resonance effect of the noble metal, and the effective utilization of visible light is realized. Therefore, the Zr-MOFs and the noble metal are compounded to realize the good and bad complementation of the two substances.
Based on the analysis, the invention selects DUT-67 as a carrier to be compounded with Pd nanosheets to construct plasmon composite photocatalyst Pd/DUT-67, and further is used for CO2Reduction and utilization of gas, etc.
Disclosure of Invention
The object of the present invention is to improve CO by using Zr-MOFs having a porous structure and a large specific surface area2The adsorption quantity provides a dispersing position for noble metal Pd, and the photoelectric conversion capacity, the light absorption capacity and the selective catalytic conversion of CO of the Zr-MOFs are improved by the Pd2And (4) performance.
In order to achieve the technical purpose, the technical scheme adopted by the invention comprises the following steps:
(1) preparation of DUT-67:
zirconium chloride was dissolved in N, N-dimethylformamide and N-methylpyrrolidone, 2, 5-thiophenedicarboxylic acid was added thereto after ultrasonic wave was made to dissolve, acetic acid was added thereto, and the mixture was transferred to a teflon-lined autoclave and subjected to solvothermal reaction to obtain white powder, i.e., DUT-67.
(2) Preparing Pd nanosheets:
and dissolving palladium chloride and potassium iodide in deionized water, adding tetraethylene glycol and polyvinylpyrrolidone, reducing by using an oil bath, and centrifugally washing to obtain the Pd nanosheet.
(3) Preparation of a plasmon composite photocatalyst Pd/DUT-67:
and (2) mixing the DUT-67 obtained in the step (1) with an ethanol solution containing polyvinylpyrrolidone by ultrasonic waves until the mixture is completely dispersed, adding a certain volume of Pd nanosheet solution, continuing stirring, transferring the mixture into a Teflon-lined high-pressure kettle after a certain time, and reacting for a certain time at a certain temperature to obtain Pd/DUT-67.
In the step (1), the usage ratio of zirconium chloride, 2, 5-thiophenedicarboxylic acid and acetic acid is 0.5 mmol: 0.34 mmol: 3.5 mL; the reaction temperature is 120 ℃, and the reaction time is 24 h.
In the step (2), the dosage proportion of the palladium chloride, the potassium iodide, the tetraethylene glycol and the polyvinylpyrrolidone is 26.6 mg: 871.3 mg: 9mL of: 160 mg; the oil bath reaction temperature is 160 ℃, the reaction time is 3 hours, and the solution is dispersed in 30mL ethanol solution after centrifugal washing.
In the step (3), the dosage proportion of the DUT-67, the polyvinylpyrrolidone and the Pd nanosheet solution is 50 mg: 10 mg: 0.1-0.7 mL; the reaction temperature is 85 ℃, the reaction time is 2 hours, and the volumes of the added Pd nano-sheet solutions are 0.1-0.7 ml respectively.
The plasmon composite photocatalyst Pd/DUT-67 prepared by the invention is used for photocatalytic reduction of CO2The use of (1).
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention prepares the Pd nanosheet by oil bath reduction, prepares the Pd/DUT-67 composite photocatalyst by simple solvothermal method, and improves the CO-to-CO ratio of the photocatalyst2Adsorption performance, light energy utilization rate and selective reduction of CO2The catalytic activity of (3).
(2) The invention greatly improves the transmission capability of interface electrons in a composite material system by utilizing the higher visible light response capability and the surface plasma resonance effect of the Pd/DUT-67 composite photocatalyst, thereby improving the CO transmission capability of the Pd/DUT-67 composite photocatalyst2The photoreduction ability of (a).
(3) The invention selects Pd/DUT-67 as photocatalyst and adsorbs CO2The molecules are attached to the surface of the photocatalyst, and under the irradiation of ultraviolet-visible light, the generated photoproduction electron-hole pairs are effectively separated to participate in the photocatalytic reduction of CO2In the process of (2), CO is efficiently removed2Is converted into CO, is simple to operate and is green and environment-friendly2And (4) processing technology.
Drawings
FIG. 1 is an XRD pattern of a DUT-67, 0.1-Pd/DUT-67, 0.3-Pd/DUT-67, 0.5-Pd/DUT-67, 0.7-Pd/DUT-67 composite photocatalyst;
FIG. 2 is an SEM image of (A) DUT-67 and (B)0.3-Pd/DUT-67 composite photocatalyst
FIG. 3 is a diagram of UV-vis of DUT-67, 0.1-Pd/DUT-67, 0.3-Pd/DUT-67, 0.5-Pd/DUT-67, 0.7-Pd/DUT-67 composite photocatalysts;
FIG. 4 is a steady state fluorescence plot of DUT-67 and 0.3-Pd/DUT-67 composite photocatalysts.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Zirconium chloride (ZrCl) used in the present invention4) 2, 5-Thiophenedicarboxylic acid (C)6H2O4S), palladium chloride (PdCl)2) Potassium iodide (KI), tetraethylene glycol (C)8H18O5) Polyvinylpyrrolidone ((C)6H9NO)n) N, N-dimethylformamide (C)3H7NO), N-methylpyrrolidone (C)5H9NO), methanol (CH)3OH), ethanol (C)2H6O) are all analytically pure and purchased from chemical reagents of national drug group, Inc
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: photocatalytic reduction of CO in a closed quartz reactor at 20 deg.C2In a reactor containing 30.0mg of photocatalyst and 100mL of H2O as proton source under UV-vis irradiation (300W Xe lamp) for 4 h. Stirring the reaction system with a magnetic stirrer, and introducing high-purity CO in the dark at least 20 minutes before illumination2(99.999%). During the photocatalytic reaction, CO was detected by gas chromatography (GC5890, Nanjing Konji apparatus) every hour2Gaseous products of the photoreduction reaction.
Example 1:
(1) preparation of DUT-67:
0.5mmol of zirconium chloride was dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, 0.34mmol of 2, 5-thiophenedicarboxylic acid was added thereto, the mixture was sonicated to dissolve, 3.5mL of acetic acid was added, and then, the mixture was transferred to an autoclave lined with Teflon and maintained at 120 ℃ for 24 hours. The white product was obtained by centrifugation, washed with N, N-dimethylformamide until the solution was colorless, washed three times with methanol and dried under vacuum at 120 ℃ for 12 hours.
(2) Preparing Pd nanosheets:
26.6mg of palladium chloride and 871.3mg of potassium iodide were weighed into a round-bottomed flask, and 1mL of H was added2And O, fully stirring to completely dissolve the O to form a dark red solution. 9.0mL of tetraethylene glycol was added immediately before the reaction, and 160mg of polyvinylpyrrolidone was added and stirred until the polyvinylpyrrolidone was dissolved. After uniform mixing, the round-bottom flask containing the wine red reaction liquid is put into an oil bath at 160 ℃ for reaction for 3 h. Finally, the dark red reaction solution is changed into a black Pd solution, and the solution is dispersed in 30mL of ethanol solution after centrifugal washing.
(3) Preparation of 0.1-Pd/DUT-67:
50mg of DUT-67 in step (1) was dispersed in 30mL of ethanol solution, 10mg of polyvinylpyrrolidone was added and stirred for 20min, followed by 0.1mL of Pd solution in step (2) and stirred for 30min, and the mixture was transferred to an autoclave lined with Teflon and held at 85 ℃ for 2 hours. After centrifugation and washing with ethanol, it was dried under vacuum at 100 ℃ for 6 hours to obtain 0.1-Pd/DUT-67.
Taking the sample in (3) to carry out photocatalytic reduction on CO2Testing and calculating CO2The gas reduced CO yield was 28.4. mu. mol/g.
Example 2:
(1) preparation of DUT-67:
0.5mmol of zirconium chloride was dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, 0.34mmol of 2, 5-thiophenedicarboxylic acid was added thereto and sonicated to dissolve, 3.5mL of acetic acid was added, and then, the mixture was transferred to an autoclave lined with Teflon and maintained at 120 ℃ for 24 hours. The white product was obtained by centrifugation, washed with N, N-dimethylformamide until the solution was colorless, washed three times with methanol and dried under vacuum at 120 ℃ for 12 hours.
(2) Preparing Pd nanosheets:
26.6mg of palladium chloride and 871.3mg of potassium iodide were weighed into a round-bottomed flask, and 1mL of H was added2And O, fully stirring to completely dissolve the O to form a dark red solution. 9.0mL of tetraethylene glycol was added immediately before the reaction, and 160mg of polyvinylpyrrolidone was added and stirred until the polyvinylpyrrolidone was dissolved. After being mixed evenly, the round bottom flask containing the wine red reaction liquid is put into oil bath with the temperature of 160 ℃ for reaction for 3 hours. Finally, the dark red reaction solution is changed into a black Pd solution, and the solution is dispersed in 30mL of ethanol solution after centrifugal washing.
(3) 0.3-preparation of Pd/DUT-67:
50mg of DUT-67 in step (1) was dispersed in 30mL of ethanol solution, 10mg of polyvinylpyrrolidone was added and stirred for 20min, followed by 0.3mL of Pd solution in step (2) and stirred for 30min, and the mixture was transferred to an autoclave lined with Teflon and held at 85 ℃ for 2 hours. After centrifugation and washing with ethanol, it was dried under vacuum at 100 ℃ for 6 hours to give 0.3-Pd/DUT-67.
Taking the sample in the step (3) for photocatalytic reduction of CO2Testing and calculating CO2The gas reduced CO yield was 48.6. mu. mol/g.
Example 3:
(1) preparation of DUT-67:
0.5mmol of zirconium chloride was dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, 0.34mmol of 2, 5-thiophenedicarboxylic acid was added thereto and sonicated to dissolve, 3.5mL of acetic acid was added, and then, the mixture was transferred to an autoclave with Teflon and kept at 120 ℃ for 24 hours. The white product was obtained by centrifugation, washed with N, N-dimethylformamide until the solution was colorless, washed three times with methanol and dried under vacuum at 120 ℃ for 12 hours.
(2) Preparing Pd nanosheets:
26.6mg of palladium chloride and 871.3mg of potassium iodide were weighed into a round-bottomed flask, and 1mL of H was added2O，Fully stirring to completely dissolve the red pigment to form a dark red solution. 9.0mL of tetraethylene glycol was added immediately before the reaction, and 160mg of polyvinylpyrrolidone was added and stirred until the polyvinylpyrrolidone was dissolved. After being mixed evenly, the round bottom flask containing the wine red reaction liquid is put into oil bath with the temperature of 160 ℃ for reaction for 3 hours. Finally, the dark red reaction solution is changed into a black Pd solution, and the solution is dispersed in 30mL of ethanol solution after centrifugal washing.
(3) Preparation of 0.5-Pd/DUT-67:
50mg of DUT-67 in step (1) was dispersed in 30mL of ethanol solution, 10mg of polyvinylpyrrolidone was added and stirred for 20min, followed by 0.5mL of Pd solution in step (2) and stirred for 30min, and the mixture was transferred to an autoclave lined with Teflon and held at 85 ℃ for 2 hours. After centrifugation and washing with ethanol, it was dried under vacuum at 100 ℃ for 6 hours to give 0.5-Pd/DUT-67.
Taking the sample in the step (3) for photocatalytic reduction of CO2Testing, calculating CO2The gas reduced CO yield was 23.6. mu. mol/g.
Example 4:
(1) preparation of DUT-67:
0.5mmol of zirconium chloride was dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, 0.34mmol of 2, 5-thiophenedicarboxylic acid was added thereto and sonicated to dissolve, 3.5mL of acetic acid was added, and then, the mixture was transferred to an autoclave lined with Teflon and maintained at 120 ℃ for 24 hours. The white product was obtained by centrifugation, washed with N, N-dimethylformamide until the solution was colorless, washed three times with methanol and dried under vacuum at 120 ℃ for 12 hours.
(2) Preparing Pd nanosheets:
26.6mg of palladium chloride and 871.3mg of potassium iodide were weighed into a round-bottomed flask, and 1mL of H was added2And O, fully stirring to completely dissolve the O to form a dark red solution. 9.0mL of tetraethylene glycol was added immediately before the reaction, and 160mg of polyvinylpyrrolidone was added and stirred until the polyvinylpyrrolidone was dissolved. After being mixed evenly, the round bottom flask containing the wine red reaction liquid is put into oil bath with the temperature of 160 ℃ for reaction for 3 hours. Finally, the dark red reaction solution is changed into black Pd solutionAnd after centrifugal washing, the mixture is dispersed in 30mL of ethanol solution.
(3) Preparation of 0.7-Pd/DUT-67:
50mg of DUT-67 in step (1) was dispersed in 30mL of ethanol solution, 10mg of polyvinylpyrrolidone was added and stirred for 20min, followed by 0.7mL of Pd solution in step (2) and stirred for 30min, and the mixture was transferred to an autoclave lined with Teflon and held at 85 ℃ for 2 hours. After centrifugation and washing with ethanol, it was dried under vacuum at 100 ℃ for 6 hours to give 0.7-Pd/DUT-67.
Taking the sample in (3) to carry out photocatalytic reduction on CO2Testing, calculating CO2The gas reduced CO yield was 15.9. mu. mol/g.
FIG. 1 is an XRD of a DUT-67, 0.1-Pd/DUT-67, 0.3-Pd/DUT-67, 0.5-Pd/DUT-67 and 0.7-Pd/DUT-67 composite photocatalyst, and a characteristic peak of the DUT-67 is clearly shown in the figure, but the characteristic peak of Pd cannot be detected, which is probably caused by the fact that the content of Pd nanosheets is low.
FIG. 2 is (A) an SEM image of a DUT-67 and (B) a 0.3-Pd/DUT-67 composite photocatalyst, wherein the DUT-67 is a forty-dihedron composed of a regular polygon with smooth edges and a hexagon, and the smooth surface of the DUT-67 is rough and is adhered with a layer of substance, which shows that the surface of the DUT-67 is successfully loaded with Pd nano-sheets.
FIG. 3 is a diagram of UV-vis of the composite photocatalyst of DUT-67, 0.1-Pd/DUT-67, 0.3-Pd/DUT-67, 0.5-Pd/DUT-67 and 0.7-Pd/DUT-67, wherein the diagram shows that the photoresponse capability of Pd/DUT-67 is enhanced and obviously red-shifted compared with DUT-67, which shows that the band gap of the catalyst is reduced, and the photocatalyst can more effectively utilize sunlight and improve the photocatalytic performance.
FIG. 4 is a steady-state fluorescence diagram of the DUT-67 and 0.3-Pd/DUT-67 composite photocatalysts, and the diagram shows that the strong emission peak of the DUT-67 is concentrated at 385nm, which indicates that the recombination probability of the photo-generated electron hole pair is very high, whereas the carrier separation efficiency of the 0.3-Pd/DUT-67 is significantly improved, which indicates that the photo-generated electron hole pair of the composite material is efficiently transferred and has higher photocatalytic activity than that of the DUT-67.
Claims (3)
1. A preparation method of a plasmon composite photocatalyst Pd/DUT-67 is characterized by comprising the following steps:
(1) preparation of DUT-67:
dissolving zirconium chloride in N, N-dimethylformamide and N-methylpyrrolidone, adding 2, 5-thiophenedicarboxylic acid, adding acetic acid after ultrasonic treatment until the zirconium chloride is dissolved, transferring the mixture into an autoclave lined with teflon, wherein the dosage ratio of the zirconium chloride to the 2, 5-thiophenedicarboxylic acid to the acetic acid is 0.5 mmol: 0.34 mmol: 3.5mL, obtaining white powder DUT-67 through solvothermal reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 24 hours;
(2) preparing Pd nanosheets:
dissolving palladium chloride and potassium iodide in deionized water, adding tetraethylene glycol and polyvinylpyrrolidone, and reducing by using an oil bath, wherein the dosage ratio of the palladium chloride to the potassium iodide to the tetraethylene glycol to the polyvinylpyrrolidone is 26.6 mg: 871.3 mg: 9mL of: 160mg, centrifuging and washing, wherein the oil bath reaction temperature is 160 ℃, and the reaction time is 3h to obtain the Pd nanosheet;
(3) preparation of the plasmon composite photocatalyst Pd/DUT-67:
mixing the DUT-67 obtained in the step (1) with an ethanol solution containing polyvinylpyrrolidone by ultrasonic waves until the mixture is completely dispersed, adding a certain volume of Pd nanosheet solution, and continuing stirring, wherein the dosage ratio of the DUT-67 to the polyvinylpyrrolidone to the Pd nanosheet solution is 50 mg: 10 mg: 0.1-0.7 mL, and after a certain period of time, transferring the mixture into an autoclave lined with Teflon to react for 2 hours at 85 ℃ to obtain Pd/DUT-67.
2. The method according to claim 1, wherein in the step (2), the solution is dispersed in 30mL of an ethanol solution after centrifugal washing.
3. Application of plasmon composite photocatalyst Pd/DUT-67 prepared by the preparation method of any one of claims 1-2 in photocatalytic reduction of CO2The use of (1).
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| CN104707658A (en) * | 2015-02-27 | 2015-06-17 | 福州大学 | Pd/metal-organic framework compound catalyst as well as preparation method and application thereof |
| CN107262153A (en) * | 2017-08-07 | 2017-10-20 | 福州大学 | A kind of preparation method of Pd/MIL 100 (Fe) photochemical catalyst |
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